WO2020108217A1 - 一种阻燃hips材料及其制备方法 - Google Patents

一种阻燃hips材料及其制备方法 Download PDF

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Publication number
WO2020108217A1
WO2020108217A1 PCT/CN2019/114369 CN2019114369W WO2020108217A1 WO 2020108217 A1 WO2020108217 A1 WO 2020108217A1 CN 2019114369 W CN2019114369 W CN 2019114369W WO 2020108217 A1 WO2020108217 A1 WO 2020108217A1
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Prior art keywords
flame retardant
flame
retardant
hips
parts
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PCT/CN2019/114369
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English (en)
French (fr)
Inventor
秦旺平
付锦锋
肖鹏
黄险波
叶南飚
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金发科技股份有限公司
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Application filed by 金发科技股份有限公司 filed Critical 金发科技股份有限公司
Priority to KR1020217011937A priority Critical patent/KR102604651B1/ko
Priority to JP2021521794A priority patent/JP7307792B2/ja
Priority to US17/286,494 priority patent/US11926725B2/en
Priority to EP19889493.3A priority patent/EP3862395B1/en
Publication of WO2020108217A1 publication Critical patent/WO2020108217A1/zh
Priority to AU2020101188A priority patent/AU2020101188A4/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/10—Extrusion moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/823—Temperature control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/72—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/488—Parts, e.g. casings, sealings; Accessories, e.g. flow controlling or throttling devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/728—Measuring data of the driving system, e.g. torque, speed, power, vibration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2793/00—Shaping techniques involving a cutting or machining operation
    • B29C2793/0027—Cutting off
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2009/00—Use of rubber derived from conjugated dienes, as moulding material
    • B29K2009/06—SB polymers, i.e. butadiene-styrene polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0026—Flame proofing or flame retarding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0016—Non-flammable or resistant to heat

Definitions

  • the invention relates to the field of flame retardant polymer materials, in particular to a flame retardant HIPS material and a preparation method thereof.
  • Flame retardant HIPS resins are widely used in audio-visual equipment housings, office equipment housings, household appliances, power conversion devices and other fields due to their good mechanical properties, processing properties and post-processing properties, good dimensional stability and low molding shrinkage.
  • halogen flame retardant HIPS There are two current flame retardant HIPS technologies, one is a halogen flame retardant system, and the other is a halogen free flame retardant system.
  • the halogen free flame retardant system is more environmentally friendly, less corrosive to the mold, and has less gas. However, it has high material cost and processing energy consumption, which limits the widespread use and promotion in the market; the general halogenated flame retardant HIPS material contains HIPS resin halogen flame retardant, antimony oxide or salt, anti-dripping agent , As well as antioxidants and other necessary processing aids, can produce products with relatively balanced rigidity, fluidity and toughness.
  • the object of the present invention is to provide a low halogen flame retardant HIPS material with stable flame retardancy and excellent appearance.
  • a flame retardant HIPS material based on parts by weight, including the following components:
  • the auxiliary flame retardant is 1,3,5-triazine compound.
  • the 1,3,5-triazine compound is a chemical substance or derivative having the following structure:
  • R 1 , R 2 , and R 3 are the same and independently represent -P(C 6 H 5 ) 2 , -P(CH 3 ) 2 , -PH 2 O 4 , -PH 2 O 2 , -SiH 3 , --SiCl 3 , -SiOH 2 , SiHCl 2 , -SiHO 3 , -((CH 3 ) 5 Si)2O, -NHR, -NR 2 , -NCH, -NO 3 , -NH 2 , -NCO, -N (CH 3 ) or -N 2 Cl.
  • the HIPS resin is a butadiene-styrene graft copolymer. Based on the total weight of the entire HIPS resin, the rubber content is 7 to 11% by weight, the melt flow rate is 200 to 5°C, and the load is 5 to 15 g/kg. min.
  • the bromine-based flame retardant is one of decabromodiphenylethane, brominated epoxy, tetrabromobisphenol A, tris(tribromophenoxy)triazine, octabromoether or imine bromide or Several mixtures.
  • the flame retardant HIPS material according to the present invention in terms of parts by weight, also includes antimony-based flame retardant synergist 1-7 parts, anti-dripping agent 0.01-2 parts, and processing aid 0-2 Copies.
  • the antimony flame retardant synergist is one or more of antimony trioxide, antimony pentoxide, sodium antimonate or antimony phosphite;
  • the anti-dripping agent is perfluoropolyolefin or styrene- Acrylonitrile-coated perfluoropolyolefin;
  • the processing aid is one or more of antioxidants, lubricants, or anti-photothermal oxidants.
  • the antioxidant is a compound of a hindered phenolic primary antioxidant and a phosphite secondary antioxidant
  • the anti-photothermal oxidant is one or a mixture of alkylated hindered polyphenols, hindered monophenols, amines, phosphites or hydroxybenzotriazole;
  • the lubricant is one or a mixture of aliphatic amide, fatty acid or salt thereof, white mineral oil, silicone oil or silicone.
  • the weight content of phosphorus element is 30 ppm-3000 ppm, and the weight content of nitrogen element is 500 ppm-50,000 ppm.
  • the test method for the weight content of the phosphorus element is as follows: 0.4g-0.6g of the sample particles to be tested are placed in a round-bottom flask, 10ml of concentrated H 2 SO 4 and 5ml of H 2 O 2 are added , and placed on an electric heating plate at 480°C It takes 35min-45min to digest until it is completely carbonized; after the carbonization is completed, it is cooled for 5min, and then the appropriate amount of H 2 O 2 is added to determine whether it is completely carbonized.
  • the test method for the weight content of the nitrogen element is: using Kjeldahl's nitrogen determination method, add a proper concentration of protein solution 1.0mL to the flask, add the analysis sample to the bottom of the flask, and then sequentially add potassium sulfate-copper sulfate 0.3g, concentrated sulfuric acid 2.0mL, 30% hydrogen peroxide 1.0Ml, heat and boil until the material in the flask is carbonized and blackened, distillation absorption of inorganic nitrogen standard sample, distillation absorption of the test sample and blank sample, after the sample is processed, use acid trace
  • the burette is titrated with a standard hydrochloric acid solution of 0.0100mol/L, and the number of milliliters of standard hydrochloric acid solution consumed for each titration is recorded. Finally, the nitrogen element content of the sample to be measured is calculated, and the value is rounded to the tenth digit.
  • the invention also provides a preparation method of the above-mentioned flame-retardant HIPS material, including the following steps:
  • the present invention has the following beneficial effects:
  • the present invention effectively reduces the amount of brominated flame retardants and the flame retardant cost through the coordinated compounding of brominated flame retardants and auxiliary flame retardants, and can achieve Stable UL 94 (1.5mm) V-0 flame retardant rating;
  • the flame retardant HIPS material provided by the present invention has a low halogen content, low gas gas, high cost performance, and avoids the formation of gas lines on the surface of the product by too much acid gas , With good appearance, can be widely used in the field of thin-walled parts, such as office equipment, film and television multimedia, household appliances, etc.
  • the raw materials used in the present invention are as follows: all are commercially available raw materials.
  • HIPS resin PS 350K, Taiwan Guoheng Company, its rubber content is 7 ⁇ 11wt%, melt flow rate is 200°C, 5 ⁇ 15g/min under 5Kg load condition;
  • Auxiliary flame retardant 1 R1, R2 and R3 are the same phosphoalkyl group (-P(CH 3 ) 2 ) or phosphate group (-PH 2 O 4 ); auxiliary flame retardant 2: R1, R2 and R3 are the same Silane group (-SiH3) or amine group (-NH2);
  • Flame retardant synergist antimony trioxide, Yiyang Yincheng mineral.
  • Anti-dripping agent 5935EF, American 3M Company.
  • the auxiliary flame retardant and different types of brominated flame retardants can achieve the V-0 flame retardant effect.
  • the two have a synergistic compounding effect, which is effective
  • the amount of brominated flame retardants is reduced, and the flame retardant cost is reduced.
  • the material can not only achieve a stable UL94 (1.5mm) V-0 flame retardant grade, but also avoid excessive acid gas on the surface of the parts It forms air lines and has a good appearance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

本发明公开了一种阻燃HIPS材料及其制备方法，包括组份：HIPS树脂90-67份；溴系阻燃剂8-15份；辅助阻燃剂3-7份；其中，所述辅助阻燃剂为1,3,5-三嗪类化合物。本发明通过溴系阻燃剂和辅助阻燃剂协同复配，有效地减少了溴系阻燃剂的用量，可达到稳定的UL94(1.5mm)V-0阻燃等级；与现有的溴系阻燃HIPS相比，具有低卤素含量，低瓦斯气，高性价比，避免了过多酸性气体在制件表面形成气纹，具有良好的外观，可广泛应用于薄壁制件领域，如办公设备，影视多媒体，家用电器领域等。

Description

一种阻燃HIPS材料及其制备方法 技术领域
本发明涉及阻燃高分子材料领域，具体涉及一种阻燃HIPS材料及其制备方法。
背景技术
阻燃HIPS树脂由于其良好的力学性能，加工性能和后加工性能，良好尺寸稳定性和较低的成型收缩率被广泛应用于视听设备外壳，办公设备外壳，家用电器，电源转换装置等领域。
目前的阻燃HIPS技术存在两种，一种为有卤阻燃体系，另一种为无卤阻燃体系，无卤阻燃体系更为环保，对模具的腐蚀性弱，瓦斯气较少，但是具有较高的材料成本及加工能耗，限制了市场上的广泛使用及推广；通常的有卤阻燃HIPS材料中含有HIPS树脂卤系阻燃剂，锑氧化物或盐，抗滴落剂，以及抗氧剂润滑剂等必须的加工助剂，可制得刚性，流动性，韧性较为平衡的产品。但是由于过高的卤系阻燃剂含量，导致材料在成型加工过程中，受热分解会产生较多的卤化氢气体，这种酸性气体会在制件表面形成气纹，影响制件的外观。
发明内容
为了克服现有技术的缺点与不足，本发明的目的在于提供一种阻燃稳定且外观优良的低卤阻燃HIPS材料。
本发明是通过以下技术方案实现的：
一种阻燃HIPS材料，按重量份计，包括以下组份：
HIPS树脂      90-67份
溴系阻燃剂    10-15份
辅助阻燃剂    3-7份
其中，所述辅助阻燃剂为1,3,5-三嗪类化合物。
所述1,3,5-三嗪类化合物为具有如下结构的化学物质或者衍生物：
Figure PCTCN2019114369-appb-000001
其中，R 1、R 2、R 3相同，彼此独立的代表-P(C 6H 5) 2、-P(CH 3) 2、-PH 2O 4、-PH 2O 2、-SiH 3、--SiCl 3、-SiOH 2、SiHCl 2、-SiHO 3、-((CH 3) 5Si)2O、-NHR、-NR 2、-NCH、-NO 3、-NH 2、-NCO、-N(CH 3)或-N 2Cl。
所述HIPS树脂为丁二烯-苯乙烯接枝共聚物，基于整个HIPS树脂的总重量，其橡胶含量为7～11wt％，熔体流动速率在200℃，5Kg载荷条件下为5～15g/min。
所述溴系阻燃剂为十溴二苯乙烷、溴化环氧、四溴双酚A、三(三溴苯氧基)三嗪、八溴醚或溴化亚胺中的一种或几种混合物。
根据实际性能需要，本发明所述的阻燃HIPS材料，按重量份数计，还包括锑系阻燃协效剂1-7份、抗滴落剂0.01-2份、加工助剂0-2份。
所述锑系阻燃协效剂为三氧化二锑、五氧化二锑、锑酸钠或亚磷酸锑中的一种或几种；所述抗滴落剂为全氟聚烯烃或苯乙烯-丙烯腈包覆的全氟聚烯烃；所述加工助剂为抗氧剂、润滑剂或抗光热氧化剂中的一种或几种。
所述抗氧剂为受阻酚类主抗氧剂和亚磷酸酯类辅抗氧剂的复配物；
所述抗光热氧化剂为烷基化受阻多酚、受阻单酚、胺类、亚磷酸酯类或羟基苯并三唑中的一种或几种的混合物；
所述润滑剂为脂肪族酰胺、脂肪酸或其盐、白矿油、硅油或聚硅酮中的一种或几种的混合物。
优选的，基于阻燃HIPS材料的总重量，磷元素的重量含量为30ppm-3000ppm，氮元素的重量含量为500ppm-50000ppm。
其中，所述磷元素的重量含量的测试方法为：取0.4g-0.6g待测样品粒子置于圆底烧瓶，加10ml浓H 2SO4和5mlH 2O 2，置于480℃的电热板进行消解直至完全碳化，需要35min-45min；碳化结束后进行冷却5min，然后加适量H 2O 2，判断是否完全碳化，未完全则继续加H 2O 2直至完全碳化，然后在100ml容量瓶中进行冷却定容，过滤，离心取上清液，然后进行电感耦合等离子体发射光谱测试ICP，数值四舍五入到十位数；
所述氮元素的重量含量的测试方法为：采用凯氏定氮法，在烧瓶中加入适当 浓度的蛋白溶液1.0mL，分析样品加到烧瓶底部，依次加入硫酸钾-硫酸铜0.3g，浓硫酸2.0mL，30％过氧化氢1.0Ml，微火加热煮沸至烧瓶内物质炭化变黑，无机氮标准样品的蒸馏吸收，待测样品和空白样品的蒸馏吸收，样品处理好之后，采用酸式微量滴定管以0.0100mol/L的标准盐酸溶液进行滴定，记录每次滴定耗用标准盐酸溶液毫升数，最后计算待测样品的氮元素含量，数值四舍五入到十位数。
本发明还提供了上述的阻燃HIPS材料的制备方法，包括以下步骤：
a，将各组份原料按配比在高速混合机充分混合3-6分钟，得到混合物；
b，将上述混合物经过精密计量的送料装置输送到双螺杆挤出机中，挤出机螺杆各段温度控制在170～220℃之间，双螺杆挤出机的长径比为30～35，螺杆转速为300-800转/分钟，在螺杆的剪切，混合，输送下，物料得以充分熔化，混合，然后经过挤出，造粒，干燥得到阻燃HIPS粒子；
c，将阻燃HIPS粒子加入到注塑机成型到所需测试的样条，注塑条件为料筒温度185-220℃，注塑压力为40-60MPa，流量为40-70cm 3/s。
本发明与现有技术相比，具有如下有益效果：
(1)本发明通过溴系阻燃剂和辅助阻燃剂协同复配，有效地减少了溴系阻燃剂的用量，降低了阻燃成本，通过气相和凝聚相复合阻燃机理，可达到稳定的UL 94(1.5mm)V-0阻燃等级；
(2)本发明所提供的阻燃HIPS材料，与现有的溴系阻燃HIPS相比，具有低卤素含量，低瓦斯气，高性价比，避免了过多酸性气体在制件表面形成气纹，具有良好的外观，可广泛应用于薄壁制件领域，如办公设备，影视多媒体，家用电器领域等。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
本发明中使用的原料如下：全部为市售原料。
HIPS树脂，PS 350K，台湾国亨公司，其橡胶含量为7～11wt％，熔体流动速率在200℃，5Kg载荷条件下为5～15g/min；
溴系阻燃剂：
十溴二苯乙烷，来源于市购；
溴化环氧，来源于市购；
溴代三嗪，来源于市购；
溴化亚胺，来源于市购；
辅助阻燃剂1：R1、R2和R3为相同的磷烷基(-P(CH 3) 2)或磷酸基(-PH 2O 4)；辅助阻燃剂2：R1、R2和R3为相同的硅烷基(-SiH3)或胺基(-NH2)；
润滑剂：EBS B50，锐驰化工。
阻燃协效剂：三氧化二锑，益阳银城矿产。
抗滴落剂，5935EF，美国3M公司。
各性能的测试标准或方法：
检测项目 单位 执行标准
阻燃性能 Class UL 94
实施例1-8及对比例1-3：阻燃HIPS材料的制备
a，将各组份原料按配比在高速混合机充分混合3-6分钟，得到混合物；
b，将上述混合物经过精密计量的送料装置输送到双螺杆挤出机中，挤出机螺杆各段温度控制在170～220℃之间，双螺杆挤出机的长径比为30～35，螺杆转速为300-800转/分钟，在螺杆的剪切，混合，输送下，物料得以充分熔化，混合，然后经过挤出，造粒，干燥得到阻燃HIPS粒子；
c，将阻燃HIPS粒子加入到注塑机成型到所需测试的样条，注塑条件为料筒温度185-220℃，注塑压力为40-60MPa，流量为40-70cm 3/s。
对阻燃HIPS材料进行性能测试，数据见表1。
表1实施例1-8及对比例1-3的具体配比(重量份)及其测试性能结果
Figure PCTCN2019114369-appb-000002
Figure PCTCN2019114369-appb-000003
从表1的实施例和对比例的比较可以看出：辅助阻燃剂与不同类型的溴系阻燃剂共同作用可以达到V-0的阻燃效果，二者具有协效复配作用，有效地减少了溴系阻燃剂的用量，降低了阻燃成本，复配后使得材料不仅可以达到稳定的UL94(1.5mm)V-0阻燃等级，且避免了过多酸性气体在制件表面形成气纹，具有良好的外观。

Claims (11)

  1. 一种阻燃HIPS材料，其特征在于，按重量份计，包括以下组份：
    HIPS树脂     90-67份
    溴系阻燃剂   10-15份
    辅助阻燃剂   3-7份
    其中，所述辅助阻燃剂为1,3,5-三嗪类化合物，为具有如下结构的化学物质或者衍生物：
    Figure PCTCN2019114369-appb-100001
    其中，R 1、R 2、R 3相同，彼此独立的代表-P(C 6H 5) 2、-P(CH 3) 2、-PH 2O 4、-PH 2O 2、-SiH 3、--SiCl 3、-SiOH 2、SiHCl 2、-SiHO 3、-((CH 3) 5Si)2O、-NHR、-NR 2、-NCH、-NO 3、-NH 2、-NCO、-N(CH 3)或-N 2Cl。
  2. 根据权利要求1所述的阻燃HIPS材料，其特征在于，所述HIPS树脂为丁二烯-苯乙烯接枝共聚物，基于整个HIPS树脂的总重量，其橡胶含量为7～11wt％。
  3. 根据权利要求1所述的阻燃HIPS材料，其特征在于，所述HIPS树脂的熔体流动速率在200℃，5Kg载荷条件下为5～15g/min。
  4. 根据权利要求1所述的阻燃HIPS材料，其特征在于，所述溴系阻燃剂为十溴二苯乙烷、溴化环氧、四溴双酚A、三(三溴苯氧基)三嗪、八溴醚或溴化亚胺中的一种或几种混合物。
  5. 根据权利要求1所述的阻燃HIPS材料，其特征在于，按重量份数计，还包括锑系阻燃协效剂1-7份、抗滴落剂0.01-2份、加工助剂0-2份。
  6. 根据权利要求5所述的阻燃HIPS材料，其特征在于，所述锑系阻燃协效剂为三氧化二锑、五氧化二锑、锑酸钠或亚磷酸锑中的一种或几种；所述抗滴落剂为全氟聚烯烃或苯乙烯-丙烯腈包覆的全氟聚烯烃；所述加工助剂为抗氧剂、润滑剂或抗光热氧化剂中的一种或几种。
  7. 根据权利要求1-6任一项所述的阻燃HIPS材料，其特征在于，基于阻燃HIPS材料的总重量，磷元素的重量含量为30ppm-3000ppm。
  8. 根据权利要求1-6任一项所述的阻燃HIPS材料，其特征在于，基于阻燃HIPS材料的总重量，氮元素的重量含量为500ppm-50000ppm。
  9. 根据权利要求7所述的阻燃HIPS材料，其特征在于，所述磷元素的重量含量的测试方法为：取0.4g-0.6g待测样品粒子置于圆底烧瓶，加10ml浓H 2SO4和5mlH 2O 2，置于480℃的电热板进行消解直至完全碳化，需要35min-45min；碳化结束后进行冷却5min，然后加适量H 2O 2，判断是否完全碳化，未完全则继续加H 2O 2直至完全碳化，然后在100ml容量瓶中进行冷却定容，过滤，离心取上清液，然后进行电感耦合等离子体发射光谱测试ICP。
  10. 根据权利要求8所述的阻燃HIPS材料，其特征在于，所述氮元素的重量含量的测试方法为：采用凯氏定氮法，在烧瓶中加入适当浓度的蛋白溶液1.0mL，分析样品加到烧瓶底部，依次加入硫酸钾-硫酸铜0.3g，浓硫酸2.0mL，30％过氧化氢1.0Ml，微火加热煮沸至烧瓶内物质炭化变黑，无机氮标准样品的蒸馏吸收，待测样品和空白样品的蒸馏吸收，样品处理好之后，采用酸式微量滴定管以0.0100mol/L的标准盐酸溶液进行滴定，记录每次滴定耗用标准盐酸溶液毫升数，最后计算待测样品的氮元素含量。
  11. 权利要求1-10任一项所述的阻燃HIPS材料的制备方法，其特征在于，包括以下步骤：
    a，将各组份原料按配比在高速混合机充分混合3-6分钟，得到混合物；
    b，将上述混合物经过精密计量的送料装置输送到双螺杆挤出机中，挤出机螺杆各段温度控制在170～220℃之间，双螺杆挤出机的长径比为30～35，螺杆转速为300-800转/分钟，在螺杆的剪切，混合，输送下，物料得以充分熔化，混合，然后经过挤出，造粒，干燥得到阻燃HIPS粒子；
    c，将阻燃HIPS粒子加入到注塑机成型到所需测试的样条，注塑条件为料筒温度185-220℃，注塑压力为40-60MPa，速度为40-70cm 3/s。
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